1. Field of the Invention
The present invention relates to novel tetracyclododecenecarboxylic acid esters and (math) acrylic acid addition products thereof and methods for producing the same.
Such tetracyclododecenecarboxylic acid esters according to the present invention have one alkyl group and one carboxylic acid ester group on a bulky bridged cyclic hydrocarbon skeleton which has excellent moisture-resistance, heat-resistance, optical characteristics, and other properties. Similarly (meth)acryl acid addition products of the tetracyclododecenecarboxylic acid esters have one carboxylic acid ester group and one (meth) acryl group on a bulky bridged cyclic hydrocarbon skeleton which has excellent moisture-resistance, heat-resistance, optical characteristics, and other properties. Thus, they are useful, for example, as a material for photosensitive resists for semiconductor fine processing or the like and a material for optical material resins.
2. Description of the Related Art
Recently, characteristic requirements for photosensitive resists and optical material resins have been increasingly diversified and heightened. For example, improvements are strongly required in capacity of photosensitive resists in fine processing corresponding to short wave lasers as well as in optical characteristics, heat resistance and mechanical strength of resins for optical materials.
It is known that when tetracyclododecenecarboxylic acid derivatives are used as a polymer component of the abovementioned photosensitive resists or optical material resins, capability in fine processing and characteristics such as transparency, moisture-resistance and heat-resistance can be improved. Accordingly, today, requirements in capabilities of tetracyclododecenecarboxylic acid derivatives for photosensitive resists and optical material resins have been also increasingly diversified and heightened.
As for tetracyclododecenecarboxylic acid derivatives, for example, Japanese Patent Application Laid-open No. 1973-49753 describes that 8-carboxymethyltetracyclo[4.4.0.12,5.17,10]-dodeca-3-ene is obtained from cyclopentadiene or methyl acrylate. Japanese Patent Application Laid-open No. 1992-198154 described that 8-methyl-8-carboxymethyltetracyclo[4.4.0.12,5.17,10]-dodeca-3-ene or 8-methyl-8-carboxyethyltetracyclo[4.4.0.12,517,10]-dodeca-3-ene are obtained by the Diels-Alder reaction with dicyclopentadiene and methyl methacrylate or ethyl methacrylate.
Further, Japanese Patent Application Laid-open No. 1998-307400 describes that t-butoxycarbonyltetracyclo[4.4.0.12,5.17,10]-3-dodecanyl methacrylate is obtained from hydroxy-8-t-butoxycarbonyltetracyclo[4.4.0.12,5.17,10]-dodecane and methacryloyl chloride. Further, Japanese Patent Application Laid-open No. 2001-11122 describes methoxycarbonyltetracyclo[4.4.0.12,5.17,10]-dodecyl methacrylate.
However, so far, there has been no report on a compound having an alkyl group on an unsaturated ring of 8-alkoxycarbonyltetracyclo[4.4.0.12,5.17,10]dodeca-3-ene skeleton or a (meth)acrylic acid addition product of this compound, namely 8-alkoxycarbonyltetracyclo[4.4.0.12,5.17,10]-3-dodecanes having a (meth)acryloyl group.
The present invention was accomplished under the abovementioned circumstances regarding tetracyclododecenecarboxylic acid derivatives. An objective of the present invention is to provide novel tetracyclododecenecarboxylic acid derivatives, in particular, novel tetracyclododecenecarboxylic acid esters and (math)acrylic acid addition products thereof, which are useful as a raw material for photosensitive resists for semiconductor fine processing or the like and as a raw material for optical material resins.
The present invention provides alkyl-substituted tetracyclododecenecarboxylic acid esters represented by the general formula (I) 
wherein R1 is an alkyl group having 1 to 4 carbon atoms and R2 is a hydrocarbon group having 1 to 12 carbon atoms.
Further, the present invention provides (meth)acrylic acid addition products of alkyl-substituted tetracyclododecenecarboxylic acid esters, represented by the general formula (II) 
wherein R1 is an alkyl group having 1 to 4 carbon atoms, R2 is a hydrocarbon group having 1 to 12 carbon atoms, and R3 is a hydrogen atom or a methyl group.
Further, the present invention provides methods of producing alkyl-substituted tetracyclododecenecarboxylic acid esters represented by the abovementioned general formula (I) characterized in that an alkylcyclopentadiene represented by the general formula (III) 
wherein R1 is an alkyl group having 1 to 4 carbon atoms
and a norbornenecarboxylic acid ester represented by the general formula (IV) 
wherein R2 is a hydrocarbon group having 1 to 12 carbon atoms are subjected to the Diels-Alder reaction.
Further, the present invention provides methods of producing (meth)acrylic acid addition products of alkyl-substituted tetracyclododecenecarboxylic acid esters represented by the abovementioned general formula (II) characterized in that an alkyl-substituted tetracyclododecenecarboxylic acid ester represented by the abovementioned general formula (I) and (meth)acrylic acid are reacted in the presence of an acid catalyst.